Über Chalkogenolate. 198. Untersuchungen über Polythiocuprate (I) [Cu(Sx)]− 2. Hydrazinium- und Ethylendiammoniumpolythiocuprate(I)

On Chalcogenolates. 198. Studies on Polythiocuprates(I) [Cu(S_x)]^?. 2. Hydrazinium and Ethylenediammonium Polythiocuprates(I) The red polythiocuprates(I) 1–5 (formulae see ?Inhaltsübersicht”?) have been prepared by reaction of hydrazinium or ethylenediammonium polysulfides with copper(II) salts, dissolved in water, under variable conditions. Their properties are described. In aqueous alkaline media 1–5 decompose into CuS and S; in the presence of carbon disulfide CuS, S_x^2?, and CS₃^2? besides CS₄^2? and S₂CO^2? are formed. The existence of the discreet ion [Cu₂CS₇]^2?, described in literature, was not confirmed. The polythiocuprates(I) 1–5 , dissolved im dimethylformamide, decompose via the radical anion S₃^?. The decomposition of S₃^? has been studied kinetically by means of compound 5 . The half-life of decay of S₃^? is τ_1/2 = 71.5 h at 20°C. The pentathiocuprate(I) 3 reacts with n-butyl chloride to produce the substituted sulfanes (C₄H₉)₂S_x′ where x = 1, 2 and 3.     

Über Chalkogenolate. 179. Kupfer(I)-thioxanthate und Thioxanthatocuprate(I)

On Chalcogenolates. 179. Copper(I) Thioxanthates and Thioxanthatocuprates(I) Copper(I) thioxanthates Cu[S₂C? SR], where R = C₂H₅, ⁿC₄H₉, and CH₂? C₆H₅, have been prepared by two procedures and studied by means of diverse methods. They are soluble in ethanolic and acetonic solutions containing the corresponding [S₂C? SR]^? ions in excess to yield thioxanthatocuprates(I) [Cu_n(S₂C? SR)_n+1]^?. The compounds [(C₆H₅)₄P][Cu_n(S₂C? SC₂H₅)_n+1] with n = 1, 4, 6 have been isolated. The existence of [(C₆H₅)₄P][Cu₄(S₂C? SC₄H₉)₅] and [(C₆H₅)₄P][Cu₆(S₂C? SCH₂? C₆H₅)₇] has been ascertained.     

Über Chalkogenolate. 197. Untersuchungen über Polythiocuprate(I) [Cu(Sx)]− 1. Eigenschaften und Reaktionen von Ammoniumtetrathiocuprat(I)

On Chalcogenolates. 197. Studies on Polythiocuprates(I) [Cu(S_x)]^?. 1. Properties and Reactions of Ammonium Tetrathiocuprate(I) The properties of NH₄[Cu(S₄)] have been studied. In watery alkaline media it decomposes into CuS and S; in the presence of carbon disulfide CuS, S_x^2?, and CS₃^2? besides CS₄^2? and S₂CO^2? are formed. The compound (NH₄)₂[Cu₂CS₇], described in literature, does not exist. In dimethylformamide dissolved NH₄[Cu(S₄)] decomposes via the radical anion S₃^?. NH₄[Cu(S₄)] reacts with n-butyl chloride to yield the substituted sulfanes (C₄H₉)₂S_x with x = 1, 2, and 3.     

Über Chalkogenolate. 163. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 2. Kristallstruktur von Dikalium-1,2-hydrazin-bis(dithioformiat)

On Chalcogenolates. 163. Reactions of Hydrazine with Carbon Disulfide. 2. Crystal Structure of Dipotassium 1,2-Hydrazine-bis (dithioformate) The title compound K₂[S₂C? NH? NH? CS₂] ( 1 ) crystallizes with Z = 4 in the orthorhombic space group Pbna with cell dimensions a = 6.635(1), b = 10.825(2), c = 12.866(2) Å. The crystal structure has been determined from single crystal X-ray data measured at ?85 °C and refined to a conventional R of 0.034 for 969 independent reflections (R_w = 0.042). The [S₂C? NH? NH? CS₂]^2? ions are linked together by hydrogen bridges N? H…?S. The K⁺ ions are surrounded by seven sulfur atoms in irregular coordination.     

Über Chalkogenolate. 101. Untersuchungen über Halbester der Monothiokohlensäure. 1. Darstellung und Eigenschaften von Oxoxanthaten

On Chalcogenolates. 101. Studies on Hemiesters of Monothiocarbonic Acid. 1. Preparation and Properties of Oxoxanthates Alkyl oxoxanthates of alkali metals have been prepared by reaction of COS with the corresponding alkoxides. The reaction of ethyl oxoxanthate with methyl iodide leads to S-methyl-O-ethyl ester of monothiocarbonic acid. The oxidation of [SOC? OC₂H₅]^? ions with iodine forms bis(ethoxycarbonyl)-disulfide (S? CO? OC₂H₅)₂. The prepared compounds have been characterized with chemical and thermoanalytical methods as well as by means of electron absorption spectra, infrared spectra, ¹H-NMR spectra, and mass spectra.     

Über Chalkogenolate. 119. Untersuchungen über N-Nitrocarbamate,N-Nitrocarbamidsäure-O-ethylester und Salze dieses Esters. Versuche zur Darstellung von N-Nitrodithiocarbamaten

On Chalcogenolates. 119. Studies on N-Nitrocarbamates, O-Ethylester of N-Nitrocarbamic Acid, and Salts of this Ester. Attempts to Prepare N-Nitrodithiocarbamates The title compounds M₂[O₂CNNO₂] with M = Na, K, and O₂N? NH? CO? OC₂H₅ as well as M[O₂NNCO? OC₂H₅] with M = NH₄, K, Rb, Cs, Ag, and Hg[O₂NNCO? OC₂H₅]₂ have been prepared. The properties and the electron absorption, infrared, ¹H and ¹³C NMR, and mass spectra are reported and discussed. Attempts to synthesize N-nitrodithiocarbamates under variable conditions were unsuccessful.     

Über Chalkogenolate. 166. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid 5. Versuche zur Darstellung von Estern der 1,2-Hydrazin-bis(dithiocarbonsäuren) [1]

On Chalcogenolates. 166. Reactions of Hydrazine with Carbon Disulfide. 5. Attempts to Prepare Esters of 1,2-Hydrazine-bis(dithiocarboxylic Acids) Possible reactions to synthesize esters of 1,2-hydrazine-bis(dithiocarboxylic acids) are described:

• 1 The reaction of K₂[S₂C? NH? NH? CS₂] with H₃CI preponderantly forms 2,5-dimethylthio-1,3,4-thiadiazole Ia and a small quantity of bis(methylthio)-ketazine II (formula see ?Inhaltsübersicht”?).
• 2 Hydrazine reacts with Cl? CS? SC₂H₅ to give exclusively compound Ib
• 3 The reaction between K₂[S₂C=N? NH? CS? SCH₃] and H₃CI yields 94% compound Ia and 6% compound II
• 4 K₂[S₂C=N? NH? CS? SCH₃] reacts with C₆H₅? CH₂Br to form a mixture containing 25% dibenzyl sulfide, 15% 2,5-dibenzylthio-1,3,4-thiadiazole I e, and 60% 2-methylthio-5-benzylthio-1,3,4-thiadiazole I d

The compounds Ia , Id and II have been characterized by means of diverse spectroscopic methods. The mechanism of the formation of compounds I has been discussed.     

Einfache Trithio- und Perthiocarbonatokomplexe mit interessanter Koordinationschemie: [E(CS3)2]2− (E = Sn,Zn, Cd), [E(CS3)3]3− (E = As,Sb, Bi,Co), {Cu(CS3)−}∞ und [Zn(CS4)2]2−

Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS₃)₂]^2? (E = Sn, Zn, Cd), [E(CS₃)₃]^3? (E = As, Sb, Bi, Co), {Cu(CS₃)^?}_∞ and [Zn(CS₄)₂]^2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh₄)₂[Zn(CS₃)₂] ( 2 ), (PPh₄)₂[Cd(CS₃)₂] ( 3 ), (PPh₄)₂[Sn(CS₃)₂] ( 4 ), (PPh₄)₃[As(CS₃)₃] ( 5 ), (PPh₄)₃[Sb(CS₃)₃] ( 6 ), (PPh₄)₃[Bi(CS₃)₃] ( 7 ), (PPh₄)₃[Co(CS₃)₃] ( 8 ) and (PPh₄)Cu(CS₃) ( 9 ) have been isolated. (PPh₄)₂[Zn(CS₄)₂] · CH₃NO₂ ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh₄)₂[C₂S₆] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, ¹¹³Cd/⁵⁹Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht.     

Über Chalkogenolate. 151. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure. 1. Darstellung und Eigenschaften von N-Thioformyldithiocarbamaten

On Chalcogenolates. 151. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 1. Synthesis and Properties of N-Thioformyl Dithiocarbamates The N-thioformyl dithiocarbamates M[S₂C? NH? CS? H], where M = K, Rb, Cs, Tl, NH₄, [N(ⁿC₄H₉)₄], Na[S₂C? NH? CS? H] · 0.5 H₂O, and Ba[S₂C? NH? CS? H]₂ · 3 HO? CH₂? CH₂? OCH₃ have been prepared by use of partial different procedures. The compounds were characterized with chemical and thermal methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-thioformyl dithiocarbamic acid were not successful.     

Über Chalkogenolate. 152. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure. 2. Kristallstruktur von Tetra-n-butylammonium-N-thioformyldithiocarbamat

On Chalcogenolates. 152. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 2. Crystal Structure of Tetra-n-butylammonium N-Thioformyl Dithiocarbamate The title compound [N(ⁿC₄H₉)₄][S₂C? NH? CS? H] crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions a = 9.694(2) Å, b = 11.478(3) Å, c = 12.551(6) Å, α = 63.03(3)°, β = 66.42(2)°, γ = 85.60(2)°. The crystal structure has been determined from single crystal X-ray data measured at 20°C and refined to a conventional R of 0.061 for 2249 independent reflections (R_w = 0.042). The structure is built up of dimeric aggregates consisting of 2[N(ⁿC₄H₉)₄]⁺ cations and 2[S₂C? NH? CS? H]^? anions. The two anions are linked together by ? CS? S…?H? N bridges. To make possible a space saving stacking of the dimeric aggregates in the crystal, one methyl group in terminal position of one n-butyl chain in the cation has gauche conformation.     

Über Chalkogenolate. 164. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 3. Synthese und Charakterisierung von Trinatrium-1,2-hydrazin-bis(dithiocarboxylat)

On Chalcogenolates. 164. Reactions of Hydrazine with Carbon Disulfide. 3. Synthesis and Characterization of Trisodium 1,2-Hydrazine-bis(dithiocarboxylate) The mixed dithiocarbamate-dithiocarbimate Na₃[S₂C? NH? N°CS₂] · 7 H₂O has been prepared by reaction of H₂N? NH₂ · H₂O with CS₂ and NaOH in aqueous solution. It has been characterized by means of diverse methods.     

Über Chalkogenolate. 93. Untersuchungen über Trithioallophansäure 2. Darstellung und Eigenschaften der freien Säure [1]

On Chalcogenolates. 93. Studies on Trithioallophanic Acid 2. Preparation and Properties of the Free Acid Yellow trithioallophanic acid H₂N? CS? NH? CS(SH) has been prepared by reaction between a suspension of K[S₂C? NH? CS? NH₂] in diethyl ether and a solution of HCl in (C₂H₅)₂O at ?15°C; the ether was distilled off at ?15°C in vacuo. The compound has been characterized by means of infrared spectra, electron absorption, ¹H-NMR spectra, and mass spectra. The dissociation constant of trithioallophanic acid in water is K_a = (1,41 ± 0,08) · 10^?2 at 20°C.     

Über Chalkogenolate. 104. Untersuchungen über Halbester der Monothiokohlensäure. 3. Kristallstruktur von Kaliummethyloxoxanthat

On Chalcogenolates. 104. Studies on Hemiesters of Monothiocarbonic Acid. 3. Crystal Structure of Potassium Methyl Oxoxanthate K[SOC? OCH₃] crystallizes with Z = 4 in the monoclinic space group P2₁/n with cell dimensions a = 6.742(5), b = 6.968(5), c = 10.777(6) Å, β = 104.6(6)°. The structure has been determined from single crystal X-ray data by means of Patterson and Fourier synthesis and refined to a final conventional R value of 0.037 using 1292 independent reflexions. The structure is built up of K⁺ and [SOC? OCH₃]^? ions. The potassium ion is bonded to four oxygen and four sulfur atoms from five oxoxanthate ions. The coordination polyhedron consists of two reciprocally penetrated and distorted O₄ and S₄ tetrahedra.     

Über Chalkogenolate. 118. Kristall- und Molekülstruktur von Oxovanadin(V)-ethylxanthat

On Chalcogenolates. 118. Crystal and Molecular Structure of Oxovanadium(V) Ethylxanthate VO[S₂C? OC₂H₅]₃ crystallizes with Z = 8 in the monoclinic space group P2₁/n with cell dimensions a = 15.065(7) Å, b = 18.540(48) Å, c = 12.824(7) Å, = 99.31(7)°. The crystal and molecular structure has been determined from single crystal X-ray data at 20°C and refined to a conventional R of 0.045.     

Magnetocaloric Properties of Heterometallic 3d–Gd Complexes Based on the [Gd(oda)3]3− Metalloligand

A series of heterometallic 3d–Gd³⁺ complexes based on a lanthanide metalloligand, [M(H₂O)₆][Gd(oda)₃] ? 3 H₂O [M=Cr³⁺ ( 1‐Cr )] (H₂oda=2,2′‐oxydiacetic acid), [M(H₂O)₆][MGd(oda)₃]₂ ? 3 H₂O [M=Mn²⁺ ( 2‐Mn ), Fe²⁺ ( 2‐Fe ) and Co²⁺ ( 2‐Co )], and [M₃Gd₂(oda)₆(H₂O)₆] ? 12 H₂O [M=Ni²⁺ ( 3‐Ni ), Cu²⁺ ( 3‐Cu ), and Zn²⁺ ( 3‐Zn )], are reported. Magnetic and heat‐capacity studies revealed a significant impact on the magnetocaloric effect depending on the anisotropy of the 3d transition metal ions, as confirmed by comparison of the observed maximum values of ?ΔS_m between complexes 2‐Co and 1‐Cr . In these two complexes, the 3d metal ions have the same spin (S=3/2 for Co²⁺ and Cr³⁺ ions), and the theoretical calculation suggested a larger ?ΔS_m value for 2‐Co (47.8 J K^?1 kg^?1) than 1‐Cr (37.5 J K^?1 kg^?1); however, the significant anisotropy of Co²⁺ ions in 2‐Co , which can result in smaller effective spins, gives a smaller value of ?ΔS_m for 2‐Co (32.2 J K^?1 kg^?1) than for 1‐Cr (35.4 J K^?1 kg^?1) at ΔH=9 T.     

Controlled Aggregation of Multiple Guanidinium Ions through a Hydrogen‐Bonded Network Assembly with Deprotonated Forms of Kemp’s Triacid

A series of five complexes that incorporate the guanidinium ion and various deprotonated forms of Kemp’s triacid (H₃KTA) have been synthesized and characterized by single‐crystal X‐ray analysis. The complex [C(NH₂)₃⁺] ? [H₂KTA^?] ( 1 ) exhibits a sinusoidal layer structure with a centrosymmetric pseudo‐rosette motif composed of two ion pairs. The fully deprotonated Kemp’s triacid moiety in 3 [C(NH₂)₃⁺] ? [KTA^3?] ( 2 ) forms a record number of eighteen acceptor hydrogen bonds, thus leading to a closely knit three‐dimensional network. The KTA^3? anion adopts an uncommon twist conformation in [(CH₃)₄N⁺] ? 2 [C(NH₂)₃⁺] ? [KTA^3?] ? 2 H₂O ( 3 ). The crystal structure of [(nC₃H₇)₄N⁺] ? 2 [C(NH₂)₃⁺] ? [KTA^3?] ( 4 ) features a tetrahedral aggregate of four guanidinium ions stabilized by an outer shell that comprises six equatorial carboxylate groups that belong to separate [KTA^3?] anions. In 3 [(C₂H₅)₄N⁺] ? 20 [C(NH₂)₃⁺] ? 11 [HKTA^2?] ? [H₂KTA^?] ? 17 H₂O ( 5 ), an even larger centrosymmetric inner core composed of eight guanidinium ions and six bridging water molecules is enclosed by a crust composed of eighteen axial carboxyl/carboxylate groups from six HKTA^2? anions.     

Über Chalkogenolate. LXX. Versuche zur Darstellung von Tetrathiooxalaten Über Alkylthio-1,3-dithiol-2-thione

On Chalcogenolates. LXX. Experiments to Prepare Tetrathiooxalates. About Alkylthio-1,3-dithiol-2-thiones Experiments to prepare tetrathiooxalates have been described. The electrolytic reduction of carbon disulfide and the reaction of sodium with CS₂ lead to formation of C₃S₅^2? ions beside others. The alkylations of C₃S₅^2? give alkylthio-l,3-dithiol-2-thiones. The formation of polymeric tetrathiooxalates has not been proved.     

Über Chalkogenolate. 128. Untersuchungen über Ester der N-Cyancarbamidsäure. 1. Darstellung und Eigenschaften der Ammoniumsalze von N-Cyancarbamidsäureestern und vom N-Methyl-N-cyancarbamidsäureethylester

On Chalcogenolates. 128. Studies on Esters of N-Cyancarbamic Acid. 1. Synthesis and Properties of Ammonium Salts of N-Cyancarbamic Acid Esters and of the Ethyl Ester of N-Methyl N-Cyancarbamic Acid The reaction of NC? N(CO? OR)₂ with NH₃(g) yields NH₄[NC? N? CO? OR], where R = CH₃, C₂H₅, and C₆H₅. NH₄[NC? N? CO? OC₂H₅] reacts with H₃CI to form NC? N(CH₃)? CO? OC₂H₅. The called compounds have been studied with chemical and spectroscopic methods.     

Über Chalkogenolate. 140. Untersuchungen über Dialkylester von Chalkogenokohlensäuren. 3. S,Se-Dialkyldithiomonoselenocarbonate Existenzbeweis von Alkylselenoxanthaten [S2C?SeR]−

On Chalcogenolates. 140. Studies on Dialkyl Esters of Chalcogenocarbonic Acids. 3. S,Se-Dialkyl Dithiomonoselenocarbonates. Evidence for the Existence of Alkyl Selenoxanthates [S₂C? SeR]^? The esters RSe? CS? SR′ with R = R′ = C₂H₅, ⁿC₃H₇ as well as with R = ⁿC₃H₇ and R′ = C₂H₅ have been produced by three different methods. The compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H, ¹³C, and ⁷⁷Se), and mass spectra. The unstable alkyl selenoxanthates M[S₂C? SeR], where M = Na, K and R = C₂H₅, ⁿC₃H₇, are formed by reaction of carbon disulfide with the corresponding alkane selenolate. Freshly prepared they react with alkyl iodides R′I to yield RSe? CS? SR′.     

Collisional activation study of cyclic polysulfides

Cyclic polysulfides isolated from higher plants, model compounds and their electron impact induced fragment ions have been investigated by various mass spectrometric methods. These species represent three sets of sulfur compounds: C₃H₆S_x (x=1?6), C₂H₄S_x (x=1?5) and CH₂S_x (x=1?4). Three general fragmentation mechanisms are discussed using metastable transitions: (1) the unimolecular loss of structural parts (CH₂S, CH₂ and S_x); (2) fragmentations which involve ring opening reactions, hydrogen migrations and recyclizations of the product ions ([M? CH₃]⁺, [M? CH₃S]⁺, [M? SH]⁺ and [M? CS₂]^+˙); and (3) complete rearrangements preceding the fragmentations ([M? S₂H]⁺ and [M? C₂H₄]^+˙). The cyclic structures of [M]^+˙ and of specific fragment ions have been investigated by comparing the collisional activation spectra of model ions. On the basis of these results the cyclic ions decompose via linear intermediates and then recyclizations of the product ions occur. The stabilities of the fragment ions have been determined by electron efficiency vs electron energy curves.